One of the biggest driving forces in cement research today is the mitigation of the CO2 emissions caused by its production. A potential solution to reduce the environmental impact is to replace cement with supplementary cementitious materials (SCMs). This replacement results in low strength at early ages because they are slow to react. The incorporation of minor elements has shown the potential to improve cement reactivity. A few percent of ZnO in C3S causes a signifi- cant increase in reactivity. This effect was related to the incorporation of zinc into the C-S-H struc- ture, which increases its needle length. This research investigates the effect of ZnO in more realis- tic systems such as alite, C3A-polyclinker, and C4AF-polyclinker. The positive effects observed in C3S are translated in the alite system, but differences were found in the polyclinkers, which have a prolonged induction period. This resulted due concentration of zinc in the interstitial phases and a small amount of zinc in alite phase. An amorphous phase was identified in the C3A polyclinker; it is believed to react rapidly with water, releasing Zn ions into the solution, which delays the reaction of alite. The addition of more gypsum controls the reaction of this phase, and thus the induction period is shortened. This work explores the possibilities of retaining Zn in alite to enhance the reactivity of more realis- tic cementitious systems. The cooling rate was critical, as a slow cooling rate promoted more Zn in the alite, less amorphous, and hence, an enhancement in the hydration of C3A-polyclinker doped with ZnO. The recalcination of this system did not affect the hydration of alite but increased the amount of crystalline C3A, which reacted faster. Thus, the amorphous phase was related to an aluminate phase. Moreover, a C4AF-polyclinker and a system with a lower amount of interstitial phase were investigated. The results showed a higher Zn concentration in alite but also extended induction periods. This was associated with the free ZnO and the amorphous content. Even when the hydration was delayed, the height of the alite peak increased with Zn doping, probably due to the incorporation of Zn into the C-S-H observed in pure C3S. In addition, the interaction between sulfates and zinc in the alite system doped with ZnO was in- vestigated. Severe retardation was observed, and the reason is proposed to be the formation of amorphous Zn compound. The presence of aluminum, ettringite formation, or an amorphous layer were discarded as the cause of the retardation.